We demonstrated large-volume three-dimensional (3D) reconstruction using plasma focused ion beam - scanning electron microscopy (PFIB-SEM). We successfully reconstructed a 750 μm (W) × 143 μm (H) × 310 μm (D) volume at a resolution of 200 nm/pix from 1,550 SEM backscattered electron images of a Li-ion battery cathode sheet. The PFIB-SEM system was found to be capable of acquiring and reconstructing larger volume 3D datasets than X-ray computed tomography, and with higher resolution and contrast.